CA2682191C - Rapid deep-section cure silicone compositions - Google Patents
Rapid deep-section cure silicone compositions Download PDFInfo
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- CA2682191C CA2682191C CA2682191A CA2682191A CA2682191C CA 2682191 C CA2682191 C CA 2682191C CA 2682191 A CA2682191 A CA 2682191A CA 2682191 A CA2682191 A CA 2682191A CA 2682191 C CA2682191 C CA 2682191C
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/14—Polysiloxanes containing silicon bound to oxygen-containing groups
- C08G77/16—Polysiloxanes containing silicon bound to oxygen-containing groups to hydroxyl groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/80—Siloxanes having aromatic substituents, e.g. phenyl side groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
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- Compositions Of Macromolecular Compounds (AREA)
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Abstract
The present invention relates to room-temperature curable silicone compositions possessing rapid deep-section cure. The silicone sealant compositions of the present invention find application in insulating glass units as elements of windows, skylights, doors and related products.
Description
RAPID DEEP-SECTION CURE SILICONE COMPOSITIONS
FIELD OF THE INVENTION
[0001] This invention is generally related to silicone compositions for structural glazing and weatherseal applications. More specifically, this invention relates to silicone rubber compositions possessing rapid deep-section cure.
BACKGROUND OF THE INVENTION
[00021 One and two-part, curable silicone compositions are well known in the art.
One-part systems generally comprise, inter alia, a silicone polymer having hydrolyzable silyl functionality and a catalyst. Upon exposure to a moist atmosphere, the silyl groups react with water to form silanol groups which, in turn, condense to form a cured siloxane network, the condensation being facilitated by the catalyst. However, silicone polymers systems typically cure slowly, i.e., after a few days to a few weeks of exposure to a moist atmosphere.
[0003] Prior art solutions to the undesirably slow deep-section cure rate of silicone and hydrocarbon based compositions include the addifon of various catalysts and other ingredients as optional components. For example, U.S. Pat. No.
4,435,536 to Kato et al. discloses one-pack, moisture-curable compositioased on hydrolyzable silyl group containing vinyl polymers wherein the inclusion of a solvent imparts storage stability and "workability" to the compositions. When cured, the compositions are said to have excellent surface hardness and weather resistance. The only specific limitation on the solvent is that it does not lead to precipitation when combined with the vinyl -------liolymeran-iPar--curing2tatalystrabd'ircan;-theitfote;--be4=hydioCatb-Ofg-alt-oh-or,--ketotiei-__ ether or ester, inter alia. Preferred solvents include alcohols and hydrolyzable esters, methanol, methyl orthoformate, ethyl orthoformate, methyltrimethoxilane and ethyl silicate being specifically illustrated. However, the systems illustrated appear to be cured at elevated temperatures as thin films and are not shown to provide deep-section cure.
Additionally, the solvents illustrated either react into the network, or are too volatile to be retained in the composition as it cures. Furthermore, long-chain alkyl alcohols which are also suggested as solvents would tend to undergo an exchange reaction with the hydrolyzable groups on silicon to effectively cap the polymer with a long-chain alkoxy group which is not readily hydrolyzed, thereby interfering with the intended moisture cure.
100041 Importantly, rapid deep-section cure is often desired in certain sealant and/or adhesive applications (e.g., construction, automotive, and insulating glass applications).
[0005] As such, there remains a need within the art for rapid deep-cure moisture-curable silicone compositions that overcome this problem.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Fig. 1 is a graphical representation of the "tack-free time" of Comparative Examples 1 and 2 and Examples 1 and 2.
[0007] Fig. 2 is a graphical representation of the "deep-section cure"
rates of Example 1 and Comparative Example 1.
[0008] Fig. 3 is a graphical representation of the "deep-section cure"
rates of Example 2 and Comparative Example 2.
FIELD OF THE INVENTION
[0001] This invention is generally related to silicone compositions for structural glazing and weatherseal applications. More specifically, this invention relates to silicone rubber compositions possessing rapid deep-section cure.
BACKGROUND OF THE INVENTION
[00021 One and two-part, curable silicone compositions are well known in the art.
One-part systems generally comprise, inter alia, a silicone polymer having hydrolyzable silyl functionality and a catalyst. Upon exposure to a moist atmosphere, the silyl groups react with water to form silanol groups which, in turn, condense to form a cured siloxane network, the condensation being facilitated by the catalyst. However, silicone polymers systems typically cure slowly, i.e., after a few days to a few weeks of exposure to a moist atmosphere.
[0003] Prior art solutions to the undesirably slow deep-section cure rate of silicone and hydrocarbon based compositions include the addifon of various catalysts and other ingredients as optional components. For example, U.S. Pat. No.
4,435,536 to Kato et al. discloses one-pack, moisture-curable compositioased on hydrolyzable silyl group containing vinyl polymers wherein the inclusion of a solvent imparts storage stability and "workability" to the compositions. When cured, the compositions are said to have excellent surface hardness and weather resistance. The only specific limitation on the solvent is that it does not lead to precipitation when combined with the vinyl -------liolymeran-iPar--curing2tatalystrabd'ircan;-theitfote;--be4=hydioCatb-Ofg-alt-oh-or,--ketotiei-__ ether or ester, inter alia. Preferred solvents include alcohols and hydrolyzable esters, methanol, methyl orthoformate, ethyl orthoformate, methyltrimethoxilane and ethyl silicate being specifically illustrated. However, the systems illustrated appear to be cured at elevated temperatures as thin films and are not shown to provide deep-section cure.
Additionally, the solvents illustrated either react into the network, or are too volatile to be retained in the composition as it cures. Furthermore, long-chain alkyl alcohols which are also suggested as solvents would tend to undergo an exchange reaction with the hydrolyzable groups on silicon to effectively cap the polymer with a long-chain alkoxy group which is not readily hydrolyzed, thereby interfering with the intended moisture cure.
100041 Importantly, rapid deep-section cure is often desired in certain sealant and/or adhesive applications (e.g., construction, automotive, and insulating glass applications).
[0005] As such, there remains a need within the art for rapid deep-cure moisture-curable silicone compositions that overcome this problem.
BRIEF DESCRIPTION OF THE DRAWINGS
[0006] Fig. 1 is a graphical representation of the "tack-free time" of Comparative Examples 1 and 2 and Examples 1 and 2.
[0007] Fig. 2 is a graphical representation of the "deep-section cure"
rates of Example 1 and Comparative Example 1.
[0008] Fig. 3 is a graphical representation of the "deep-section cure"
rates of Example 2 and Comparative Example 2.
2 SUMMARY OF THE INVENTION
100091 The present invention discloses blends of siloxane polymers and zinc oxide and their uses in sealant formulations possessing rapid deep-section cure. More particularly, the present invention provides a curable sealant composition comprising:
a) at least one silanol-terminated diorganopolysiloxane;
b) at least one crosslinker for the silanol-terminated diorganopolysiloxane(s);
c) at least one catalyst for the crosslinking reaction;
d) a rapid deep-section curing amount zinc oxide; and, optionally, e) at least one additional component selected from the group consisting of alkyl-terminated diorganopolysiloxane, filler, UV stabilizer, antioxidant, adhesion promoter, cure accelerator, thixotropic agent, plasticizer, moisture scavenger, pigment, dye, surfactant, solvent and biocide.
[0010] The room-temperature curable one and two part sealant compositions of the present invention inventively provides rapid deep-section cure.
DETAIL DESCRIPTION OF THE INVENTION
[00111 The present invention discloses blends of siloxane polymers and zinc oxide and their uses in sealant formulations. The presence of zinc oxide in silicone systems to provide high thermal conductivity and prolonged surface oil on room temperature vulcanizable (RTV) silicone sealant has been reported in U.S.
Patents Nos.
5,292,606 and 5,733,960, respectively.
_____________ e_atol:Td:EFreitIthiZIrrifiiiirialaiireonTpTisitions:can7b-e7expres.sed ii-s-the"tack-frte time" orsutface -curing and "deep-section cure" or curing along-the sealant's thickness. Tack-free time is tested by spreading a sealant to a desired thickness TM
(e.g., 6.35 mm) on a Teflon mold and placing a I Og stainless steel (SS) weight on the
100091 The present invention discloses blends of siloxane polymers and zinc oxide and their uses in sealant formulations possessing rapid deep-section cure. More particularly, the present invention provides a curable sealant composition comprising:
a) at least one silanol-terminated diorganopolysiloxane;
b) at least one crosslinker for the silanol-terminated diorganopolysiloxane(s);
c) at least one catalyst for the crosslinking reaction;
d) a rapid deep-section curing amount zinc oxide; and, optionally, e) at least one additional component selected from the group consisting of alkyl-terminated diorganopolysiloxane, filler, UV stabilizer, antioxidant, adhesion promoter, cure accelerator, thixotropic agent, plasticizer, moisture scavenger, pigment, dye, surfactant, solvent and biocide.
[0010] The room-temperature curable one and two part sealant compositions of the present invention inventively provides rapid deep-section cure.
DETAIL DESCRIPTION OF THE INVENTION
[00111 The present invention discloses blends of siloxane polymers and zinc oxide and their uses in sealant formulations. The presence of zinc oxide in silicone systems to provide high thermal conductivity and prolonged surface oil on room temperature vulcanizable (RTV) silicone sealant has been reported in U.S.
Patents Nos.
5,292,606 and 5,733,960, respectively.
_____________ e_atol:Td:EFreitIthiZIrrifiiiirialaiireonTpTisitions:can7b-e7expres.sed ii-s-the"tack-frte time" orsutface -curing and "deep-section cure" or curing along-the sealant's thickness. Tack-free time is tested by spreading a sealant to a desired thickness TM
(e.g., 6.35 mm) on a Teflon mold and placing a I Og stainless steel (SS) weight on the
3 sealant at different intervals of time. The tack free time is the time when no material sticks to the surface of the weight. Alternatively, "deep-section cure" or curing along the thickness is tested based on the spread material being cut along the thickness periodically _to_detect_the complete curing. The time taken for the material to cure completely along - _ _ _ _ _ _ ________ th __ thidlcness is called deep-section-cure; alsolcnown-as-"tlak-section-cure-."'A-p-difft-o¨m visual observation the inventors have devised a method to measure the deep-section cure, more fully described herein below, by extracting the uncured material of the sealant by solvent.
[0013] A general description of each of the components of the deep-section cure sealant composition are given as follows:
[0014] The curable composition of the present invention includes at least one silanol-terminated diorganopolysiloxanes (a). Suitable silanol-terminated diorganopolysiloxanes (a) include those of the general formula:
MaDbDic wherein "a" is 2, and "b" is equal to or greater than 1 and "c" is zero or positive; M is (H0)3....yR I õR2yS i 01/2 wherein "x" is 0, 1 or 2 and "y" is either 0 or 1, subject to the limitation that x + y is less than or is equal to 2, RI and R2 each independently is a monovalent hydrocarbon group up to 60 carbon atoms; D is R3R4SiOtr2;
wherein Wand R4 eachindependently is a monovalent hydrocarbon group up to 60 carbon atoms; and D' is R5R6Si02/2 =
[0013] A general description of each of the components of the deep-section cure sealant composition are given as follows:
[0014] The curable composition of the present invention includes at least one silanol-terminated diorganopolysiloxanes (a). Suitable silanol-terminated diorganopolysiloxanes (a) include those of the general formula:
MaDbDic wherein "a" is 2, and "b" is equal to or greater than 1 and "c" is zero or positive; M is (H0)3....yR I õR2yS i 01/2 wherein "x" is 0, 1 or 2 and "y" is either 0 or 1, subject to the limitation that x + y is less than or is equal to 2, RI and R2 each independently is a monovalent hydrocarbon group up to 60 carbon atoms; D is R3R4SiOtr2;
wherein Wand R4 eachindependently is a monovalent hydrocarbon group up to 60 carbon atoms; and D' is R5R6Si02/2 =
4 wherein R5 and R6 each independently is a monovalent hydrocarbon group up to carbon atoms.
[0015] In one embodiment of the invention, the level of incorporation of the diorganopolysiloxane wherein the silicon atom at each polymer chain end is silanol terminated (a) ranges from about 5 weight percent to, about 95 weight percent of the total composition. In another embodiment of the invention, the level of incorporation of the diorganopolysiloxane polymer or blends of diorganopolysiloxane polymers (a) ranges from about 20 weight percent to about 85 weight percent of the total composition. In yet another embodiment of the present invention, the diorganopolysiloxane polymer or blends of diorganopolysiloxane polymers (a) ranges from about 30 weight percent to about 60 weight percent of the total composition.
[0016] Suitable cross-linkers (b) of the present invention include an alkylsilicate of the general formula:
(R70)(R80)(R90)(RI O)Si where R7, R8, R9 and RI9are independently chosen monovalent C1 to C60 hydrocarbon radicals.
[0017] Other suitable crosslinkers include, but are not limited to, tetra-N-propylsilicate (NPS), tetraethylortho silicate and methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and similar alkyl substituted alkoxysilane compositions, and the like.
[0018] In one embodiment of the present invention, the level of incorporation of _the_alkylsilicate.(crosslinker)..ranges_from_aboutØ1 weight.percentto.about.10..weight_ _percent ofiiii_total composition. In another embodiment of the invention, the level of _ incorporation of the alkylsilicate (crosslinker) ranges from about 0.3 weight percent to about 5 weight percent of the total composition. In yet another embodiment of the present invention, the level of incorporation of the allcylsilicate (crosslinker) ranges from about 0.5 weight percent to about 1.5 weight percent of the total composition.
[00191 Suitable catalysts (c) for use herein can be any of those known to be useful for facilitating crosslinking in silicone sealant compositions. The catalyst may include metal and non-metal catalysts. Examples of the metal portion of the metal condensation catalysts useful in the present invention include tin, titanium, zirconium, lead, iron cobalt, antimony, manganese, bismuth and zinc compounds.
=
[0020) According to one embodiment of the present invention, tin compounds useful for facilitating crosslinking in silicone sealant compositions include:
tin compounds such as dibutyltindilaurate, dibutyltindiacetate, dibutyltindimethoxide, tinoctoate, isobutyltintriceroate, dibutyltinoxide, solubilized dibutyl tin oxide, dibutyltin bis-diisooctylphthalate, bis-tripropoxysilyl dioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyl tin tris-uberate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin di-neodecanoate, triethyltin tartarate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltintri-2-ethylhexylhexoate, tinbutyrate, and diorganotin bis P-diketonates, and the like.
[00211 In one embodiment of the invention, the catalyst for the crosslinlcing reaction is a metal catalyst. In another embodiment of the invention, the metal catalyst is selected from the group consisting of tin compounds, and in yet another embodiment of the invention, the metal catalyst is solubilized dibutyl tin oxide.
[0022) According to another embodiment of the present invention, titanium compounds useful for facilitating crosslinking in silicone sealant compositions include:
TM= ---_-_=Di(isopropoxide)iTitaniumzhis(ethylac.etoacetate)413tupont;17.T_yzorD_C];:Di( isob.utoxide):
TM
Titanium bis(ethy-lacetoacitatO) [Johnson Matthey; Vertic-KE61; Di(n-butoxide) - -Titanium bis(ethylacetoacetato) [Johnson Matthey]; 1,3-propariediokytitanium bis(ethylacetoacetate); Titanium (triethanolaminato)isopropoxide [Dupont;
Tyzor TE];
TM
Bis( triethanolarnino) titanium di (methyl diglycolate) [Sarunar; Isocat ETAM]; Titanium diisopropoxide (bis-2,4-pentanedionate) [Dupont; Tyzor AA]; Titanium ethoxide isopropoxide bis-(2,4-pentanedionate) [Satunar; Isocat AA 65]; Titanium bis-(2,4-pentanedionate) (2-EHA) [Johnson Matthey, Vertec XL100]; and tetra-allcyl titanates, for example, tetra n-butyl titanate and tetra-isopropyl titariate, and the like.
[0023] According to one specific embodiment of the invention, the catalyst for the crosslinking reaction is Di(isopropoxide) Titanium bis(ethylacetoacetate).
[0024] In one embodiment of the invention, the level of incorporation of the catalyst ranges from about 0.001 weight percent to about 1 weight percent of the total composition. In another embodiment off the invention, the level of incorporation of the catalyst, ranges from about 0.003 weight percent to about 0.5 weight percent of the total composition. In yet another embodiment of the invention, the level of incorporation of the catalyst, ranges from about 0.005 weight percent to about 0.2 weight percent of the total composition.
[0025] The curable sealant composition of the present invention provides room-temperature curable silicone sealant composition, which cures to provide rapid deep-section cure. This rapid deep-section cure is provided by the presence of particulate zinc oxide (d) in the room temperature-curable silicone sealant composition when present in an amount of at least about 1 parts by weight per 100 parts by weight of the total composition of the room-temperature curable silicone sealant composition. In one specific embodiment of the invention, the zinc oxide is present in amounts from about 2 to about 30 parts by weight per 100 parts by weight of the total composition, and in a more specific embodiment from about 5 to about 20 parts by weight per 100 parts by -Nireight-ofthe-total:composition.
[0026] The particulate zinc oxide (d) of the present invention possesses an average particle size of less than about 1 micron, from about 50 to about 70 urn, and a surface area from about 5 to about 30 m2/g. The zinc oxide (d) possesses a purity of from about 80 to about 99.9 percent and a pH that ranges from about 7.0 to about 9Ø The TM
zinc oxide of the present invention is commercially available as White Seal (IP 100) TM
(available from MLA group of Industries, Kanpur, India); Zincosil NK-T-1 50 (available from MLA group of Industries, Kanpur, India); Zincosil AH-90 (available from MLA
group of Industries, Kanpur, India); ACS (available from Aldrich Chemical Co.); Zinc oxide nano powder (available from Aldrich Chemical Co.).
[0027] According to a specific embodiment of the invention, the room-temperature curable silicone sealant composition is obtained as a "one-part"
composition, wherein all the ingredients are contained in one package and curing occurs upon exposure to atmospheric air.
[0028] According to another embodiment of the invention, the room-temperature curable silicone sealant composition is obtained using a "two-part"
composition, such compositions are well known in the art. In a two-part system the first part comprises polydiorganosiloxane as described herein, and zinc oxide, and a second part comprises a crosslinker, such as the one described herein above. The second part can also contain filler and a curing catalyst for the room-temperature curable silicone composition. The particulate zinc oxide can be added to either the first or second part. The "parts" of these two-part compositions are stored in separate packages to prevent premature curing which can occur if all the ingredients are mixed for too long a time period before the use of the composition.
[0029] Furthermore, the compositions of the present invention can be prepared using either batch or continuous modes of manufacture. Preferably, the ingredients such as silicone polymer, zinc oxide, cure catalyst, crosslinker, adhesion promoter, plasticizers, filler, process aids, and other additives are combined in a continuous compounding extruder to produce the desired sealant composition. Both the "first part"
and the "second part" are prepared in this manner. The continuous compounding extruder can be any continuous compounding extruder such as the twin screw Werner-Pfleiderer extruder, or a Buss, or P.B. Kolcneader extruder.
=
[0030] In the broadest conception of the present invention, all the ingredients may be mixed in the continuous compounding extruder, that is silicone polymer, zinc oxide, _plasticizer, a_condensation catalyst and an adhesion promoter, etc. In such a process, _ _ _ _ _ .7---------whichis;continuousT.theg.extruderAsT,operatedataTrange;_of-.20-1-.tor2002-utmore -_ preferably in the range of 25 to 50 C and the extruder is operated at a partial vacuum so as to remove volatiles during the mixing process.
[0031]
According to one embodiment of the invention, the silicone compositions of the present invention further comprise an alkoxysilane or blend of alkoxysilanes as an adhesion promoter. In one embodiment, the adhesion promoter may be a combination blend of n-2-aminoethy1-3-aminopropyltrimethoxysilane and 1,3,5-tris(trimethoxysilylpropyl)isocyanurate. Other adhesion promoters useful in the present invention include but are not limited to n-2-aminoethy1-3-aminopropyltriethoxysilane, y-aminopropyltriethoxysilane, y-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, bis-y-trimethoxysilypropypamine, N-Phenyl-y-aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, y-aminopropylmethyldiethoxysilane, y- aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, y-glycidoxypropylethyldimethoxysilane, y-glycidoxypropyltrimethoxysilane, y-gl ycidoxyethyltrimethoxysilane, 13-(3,4-epoxycyclohexyl)propyltrimethoxysilane,13-(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, f3-cyanoethyltrimethoxysilane, y-acryloxypropyltrimethoxysilane, y-methacryloxypropylmethyldimethoxysilane, 4-amino-3,3,-dimethylbutyltrimethoxysilane, and n-ethyl-3-trimethoxysily1-2-methylpropanamine, and the like.
[0032] The level of incorporation of the alkoxysilane (adhesion promoter) ranges from about 0.1 weight percent to about 20 weight percent. In one embodiment of the invention, the adhesion promoter ranges from about 0.3 weight percent to about weight percent of the total composition. In another embodiment of the invention, the adhesion promoter ranges from about 0.5 weight percent to about 2 weight percent of the total composition.
100331 In one embodiment of the invention the composition of the present invention includes a plasticizer to reduce the modulus of the cured elastomer.
The plasticizer can be polydimethylsiloxane having terminal trioganosiloxy units where the organo groups are methyl, vinyl or phenyl or combinations of these groups. For example, the polydimethylsiloxanes used as plasticizers or modulus reducing agents can normally have a viscosity of from 100 to 100,000 mpa.s measured at 25 C and can be used in amounts up to 80 parts by weight per 100 parts by weight of the polymeric material.
100341 The silicone composition of the present invention may also comprise a filler. Suitable fillers of the present invention include, but are not limited to, ground, precipitated and colloidal calcium carbonates which is treated with compounds such as stearate or stearic acid, reinforcing silicas such as fumed silicas, precipitated silicas, silica gels and hydrophobized silicas and silica gels; crushed and ground quartz, alumina, aluminum hydroxide, titanium hydroxide, diatomaceous earth, iron oxide, carbon black and graphite or clays such as kaolin, bentonite or montmorillonite, talc, mica, nano-clays, organo-clays, and the like.
[00351 In one embodiment of the present invention, the filler is a calcium carbonate filler, silica filler or a mixture thereof. In another specific embodiment of the invention, zinc oxide (d) is added directly to the filler. The type and amount of filler added depends upon the desired physical properties for the cured silicone composition.
In another embodiment of the invention, the amount of filler is from 0 weight percent to ---about-90-weight percent of-the-totakompositionr-In-yet-another embodiment-of---- ¨
¨
- ¨ -invention, -the amount of filler is from about 5 weight percent to about 60 weight percent of the total composition. In still another embodiment of the invention, the amount of filler is from about 10 weight percent to about 40 weight percent of the total composition.
The filler may be a single species or a mixture of two or more species.
[0036] The compositions of the present invention may optionally comprise non-ionic surfactant compound selected from the group of surfactants consisting of polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers of ethylene oxide (E0) and propylene oxide (PO) and copolymers of silicones and polyethers (silicone polyether copolymers), copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof in an 'amount ranging from slightly above 0 weight percent to about 10 weight percent, more preferably from about 0.1 weight percent to about 5 weight percent, and most preferably from about 0.5 weight percent to about 0.75 weight percent of the total composition.
[0037] The compositions of the present invention may be prepared using other ingredients that are conventionally employed in room temperature vulcanizing (RTV) silicone compositions such as colorants and pigments as long as they do not interfere with the desired properties.
[0038] The rapid deep-section curing silicone sealant compositions of the present invention find numerous uses in applications where rapid deep-section curing is essential.
For example, the compositions are used for weather sealing and sealant composition in insulating glass units, or IG units, as elements of windows, skylights, doors and related products, including vehicles. Additional uses of the rapid deep-section curing silicone sealant compositions include conventional curtain wall cladding systems and adjacently jointed window panels, e.g., atrium skylights, glass window walls, and the like.
Together with rapid deep-section curing the present compositions provide the necessary flexibility and resiliency, in the desired application, which provides for expansion and contraction due to various conditions, e.g., temperature variations and movement due to =---=building-settlement-and=thelike. - ¨ - - - - - - - ¨ ---------= - -[0039] The invention is illustrated by the following non-limiting examples:
Preparation of Comparative Example 1 and 2 sealant formulations:
Materials Amount in grams (g) Silanol (30000cst) 34 = OMYACARBTm FT- CaCO3 50 ZnO 0 Double treated fumed silica 6 Dimethylpolysiloxane Plasticizer 10 [0040] Comparative Examples 1 and 2 were prepared without zinc oxide and consisted of the various ingredients displayed in Table 1. Comparative Example I and 2 were prepared the same way in Ross mixer using the following procedure: 34g of silanol polymer was placed in the Ross mixer and lOg of plasticizer was placed in a Ross kettle.
Heat was applied to 100 C. 20 g of Omya CaCO3 was slowly added while mixing.
2g of doubly treated fumed silica was also added. Mixing continued for 15 minutes. The dispersion was checked. Additional 15g of Omya CaCO3 was slowly added along with 2g of doubly treated fumed silica and mixed for 30 minutes. The dispersion was again checked. Another 15g of Omya CaCO3 slowly added to the mix, along with 2 more grains of doubly treated fumed silica and mixing continued for 2 hours. The mixture was transferred to an air-tight container.
100411 Curing Procedure: The mixtures were then blended with catalyst, cross-linker and adhesion promoter with quantities and ingredients displayed in Table 2 and Table 3, respectively, and placed in a Hauschild speed mixer and kept for 9-14 days for aging. The mixtures of Comparative Examples 1 and 2 were then removed and poured in Teflon molds with 1/4" depth.
[0042] Comparative Example 1 was prepared with cross-linker methyl trimethoxy silane (MTMS) and adhesion promoter tris (trimethoxy silyl propyl) isocyanurate (Iso-T) as displayed in Table 2:
Comp. Ex. 1 Hanoi +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker MTMS 0.9 g Adhesion promoter Iso-T 0.2 g [0043] Comparative Example 2 was prepared exactly as Comparative Example 1 except that cross-linker vinyl trimethoxy silane (VTMS) and adhesion promoter Iso-T
were used as displayed in Table 3:
Comp. Ex. 2 Silanol +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker VTMS 0.9 g Adhesion promoter Iso-T 0.2 g [0044] Preparation of Example 1 sealant formulation:
Materials Amount in grams (g) Silanol (30000cst) 33 OMYACARB FT- CaCO3 45 ZnO 5 Double treated fumed silica 6 Dimethylpolysiloxane Plasticizer 10 [0045] Example 1 sealant formulation was prepared with zinc oxide and the -variousingredientsslisplayedin,Table LL_Example_Lwas prepared_in Ross_mixer_using _ _ __ the following procedure: 34g of silanol polymer was placed in a Ross mixer and lOg of plasticizer in a Ross kettle. Heat was applied to 100 C. 15 g of Omya CaCO3, 2g of doubly treated fumed silica, and 5g of zinc oxide were slowly added while mixing.
Mixing continued for 15 minutes. The dispersion was checked. An additional 15g of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture.
Mixing proceeded for 30 minutes. The dispersion was checked. Another 15g of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture.
Mixing continued for 2 hours. The mixture was transferred in an air tight container.
[00461 Curing Procedure: The mixture was then blended with catalyst, cross-linker and adhesion promoter with quantities and ingredients displayed in Table 5, in a Hauschild speed mixer and kept for 9-14 days for aging. The mixture was then taken out and poured in a Teflon mold with 'A" depth.
[0047] Example 1 was prepared cross-linker MTMS and adhesion promoter Iso-T:
Example 1 Silanol +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker MTMS 0.9 g Adhesion promoter Iso-T 0.2 g [00481 The ingredients of Example 2 sealant formulation are displayed in Table 6:
Materials Amount in grams (g) Silanol (30000cst) 34 OMYACARB FT- CaCO3 40 ZnO 10 Double treated fiuned silica 6 ..-Dimethylpolysiloxane-Plasticizer- - - --1-0. ¨ ¨ =
[0049] Example 2 sealant formulation was prepared with zinc oxide and the various ingredients displayed in Table 6. Example 2 was prepared in Ross mixer using the following procedure: 34g of Silanol polymer was placed in a Ross mixer and 10g of plasticizer was placed in a Ross kettle. Heat was applied to 100 C. 15 g of Omya CaCO3, 2g of doubly treated fumed silica, and lOg of zinc oxide were slowly added while mixing. Mixing continued for 15 minutes. The dispersion was checked. An additional lOg of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture. Mixing proceeded for 30 minutes. The dispersion was checked. Another 15g of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture.
Mixing continued for 2 hours. The mixture was transferred in an air tight container.
(00501 Curing Procedure: The mixture was then blended with catalyst, cross-linker and adhesion promoter with quantities and ingredients displayed in Table 7, in a Hauschild speed mixer and kept for 9- 14 days for aging. The mixture was then taken out and poured in a Teflon mold with 1/4" depth.
[0051] Example 2 was prepared with cross-linker vinyltrimethoxysilane (VTMS) and adhesion promoter Iso-T and the various ingredients of Table 7:
Example 2 Silanol +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker VTMS 0.9 g Adhesion promoter Iso-T 0.2 g [0052] Tack Free Time and Deep Section Cure measurements: After applying Examples 1-2 and Comparative Examples 1-2 in Teflon molds with V," thickness, the surface was made even with an aluminum spacer. Beginning at the time the material was first applied, the surface was checked with a 10g weight to determine if the material is -tackzfree-at45-minute,intervals-Iminimum)Aintilit-is-foundqolbelack=free:--qack-free¨
time data of Examples 1-2 and Comparative Examples 1-2 is presented in Figure 1.
[0053] Deep-section cure was determined by solvent swelling experiments as follows: A weighed portion of the resin in accordance with Examples 1-2 and Comparative Examples 1-2 was obtained from a cut along the thickness of the mold (a sample of about 5 grams from each of Examples 1-2 and Comparative Examples 1-2 was obtained) and allowed to swell in 100m1 of toluene for 3 days. The samples from Example 1-2 and Comparative Examples 1-2 were removed from the toluene and kept for drying under ambient conditions for 3 days. Each sample was weighed again after drying. The difference in weight provides the amount of uncured sample from Example 1-2 and Comparative Examples 1-2 dissolved in toluene. This measurement was obtained at the 6th, 24th and 48th hour after applying the sealant examples in the Teflon mold. The percentage of uncured example was plotted against time.
(0054] Deep-section cure data for Comparative Example 1 and Example 1 are presented in Figure 2, and deep-section cure data for Comparative Example 2 and Example 2 are presented in Figure 3.
(0055] While the process of the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out the process of the invention but that the invention will include all embodiments falling within the scope of the appended claims.
[0015] In one embodiment of the invention, the level of incorporation of the diorganopolysiloxane wherein the silicon atom at each polymer chain end is silanol terminated (a) ranges from about 5 weight percent to, about 95 weight percent of the total composition. In another embodiment of the invention, the level of incorporation of the diorganopolysiloxane polymer or blends of diorganopolysiloxane polymers (a) ranges from about 20 weight percent to about 85 weight percent of the total composition. In yet another embodiment of the present invention, the diorganopolysiloxane polymer or blends of diorganopolysiloxane polymers (a) ranges from about 30 weight percent to about 60 weight percent of the total composition.
[0016] Suitable cross-linkers (b) of the present invention include an alkylsilicate of the general formula:
(R70)(R80)(R90)(RI O)Si where R7, R8, R9 and RI9are independently chosen monovalent C1 to C60 hydrocarbon radicals.
[0017] Other suitable crosslinkers include, but are not limited to, tetra-N-propylsilicate (NPS), tetraethylortho silicate and methyltrimethoxysilane (MTMS), vinyltrimethoxysilane (VTMS) and similar alkyl substituted alkoxysilane compositions, and the like.
[0018] In one embodiment of the present invention, the level of incorporation of _the_alkylsilicate.(crosslinker)..ranges_from_aboutØ1 weight.percentto.about.10..weight_ _percent ofiiii_total composition. In another embodiment of the invention, the level of _ incorporation of the alkylsilicate (crosslinker) ranges from about 0.3 weight percent to about 5 weight percent of the total composition. In yet another embodiment of the present invention, the level of incorporation of the allcylsilicate (crosslinker) ranges from about 0.5 weight percent to about 1.5 weight percent of the total composition.
[00191 Suitable catalysts (c) for use herein can be any of those known to be useful for facilitating crosslinking in silicone sealant compositions. The catalyst may include metal and non-metal catalysts. Examples of the metal portion of the metal condensation catalysts useful in the present invention include tin, titanium, zirconium, lead, iron cobalt, antimony, manganese, bismuth and zinc compounds.
=
[0020) According to one embodiment of the present invention, tin compounds useful for facilitating crosslinking in silicone sealant compositions include:
tin compounds such as dibutyltindilaurate, dibutyltindiacetate, dibutyltindimethoxide, tinoctoate, isobutyltintriceroate, dibutyltinoxide, solubilized dibutyl tin oxide, dibutyltin bis-diisooctylphthalate, bis-tripropoxysilyl dioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyl tin tris-uberate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin di-neodecanoate, triethyltin tartarate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltintri-2-ethylhexylhexoate, tinbutyrate, and diorganotin bis P-diketonates, and the like.
[00211 In one embodiment of the invention, the catalyst for the crosslinlcing reaction is a metal catalyst. In another embodiment of the invention, the metal catalyst is selected from the group consisting of tin compounds, and in yet another embodiment of the invention, the metal catalyst is solubilized dibutyl tin oxide.
[0022) According to another embodiment of the present invention, titanium compounds useful for facilitating crosslinking in silicone sealant compositions include:
TM= ---_-_=Di(isopropoxide)iTitaniumzhis(ethylac.etoacetate)413tupont;17.T_yzorD_C];:Di( isob.utoxide):
TM
Titanium bis(ethy-lacetoacitatO) [Johnson Matthey; Vertic-KE61; Di(n-butoxide) - -Titanium bis(ethylacetoacetato) [Johnson Matthey]; 1,3-propariediokytitanium bis(ethylacetoacetate); Titanium (triethanolaminato)isopropoxide [Dupont;
Tyzor TE];
TM
Bis( triethanolarnino) titanium di (methyl diglycolate) [Sarunar; Isocat ETAM]; Titanium diisopropoxide (bis-2,4-pentanedionate) [Dupont; Tyzor AA]; Titanium ethoxide isopropoxide bis-(2,4-pentanedionate) [Satunar; Isocat AA 65]; Titanium bis-(2,4-pentanedionate) (2-EHA) [Johnson Matthey, Vertec XL100]; and tetra-allcyl titanates, for example, tetra n-butyl titanate and tetra-isopropyl titariate, and the like.
[0023] According to one specific embodiment of the invention, the catalyst for the crosslinking reaction is Di(isopropoxide) Titanium bis(ethylacetoacetate).
[0024] In one embodiment of the invention, the level of incorporation of the catalyst ranges from about 0.001 weight percent to about 1 weight percent of the total composition. In another embodiment off the invention, the level of incorporation of the catalyst, ranges from about 0.003 weight percent to about 0.5 weight percent of the total composition. In yet another embodiment of the invention, the level of incorporation of the catalyst, ranges from about 0.005 weight percent to about 0.2 weight percent of the total composition.
[0025] The curable sealant composition of the present invention provides room-temperature curable silicone sealant composition, which cures to provide rapid deep-section cure. This rapid deep-section cure is provided by the presence of particulate zinc oxide (d) in the room temperature-curable silicone sealant composition when present in an amount of at least about 1 parts by weight per 100 parts by weight of the total composition of the room-temperature curable silicone sealant composition. In one specific embodiment of the invention, the zinc oxide is present in amounts from about 2 to about 30 parts by weight per 100 parts by weight of the total composition, and in a more specific embodiment from about 5 to about 20 parts by weight per 100 parts by -Nireight-ofthe-total:composition.
[0026] The particulate zinc oxide (d) of the present invention possesses an average particle size of less than about 1 micron, from about 50 to about 70 urn, and a surface area from about 5 to about 30 m2/g. The zinc oxide (d) possesses a purity of from about 80 to about 99.9 percent and a pH that ranges from about 7.0 to about 9Ø The TM
zinc oxide of the present invention is commercially available as White Seal (IP 100) TM
(available from MLA group of Industries, Kanpur, India); Zincosil NK-T-1 50 (available from MLA group of Industries, Kanpur, India); Zincosil AH-90 (available from MLA
group of Industries, Kanpur, India); ACS (available from Aldrich Chemical Co.); Zinc oxide nano powder (available from Aldrich Chemical Co.).
[0027] According to a specific embodiment of the invention, the room-temperature curable silicone sealant composition is obtained as a "one-part"
composition, wherein all the ingredients are contained in one package and curing occurs upon exposure to atmospheric air.
[0028] According to another embodiment of the invention, the room-temperature curable silicone sealant composition is obtained using a "two-part"
composition, such compositions are well known in the art. In a two-part system the first part comprises polydiorganosiloxane as described herein, and zinc oxide, and a second part comprises a crosslinker, such as the one described herein above. The second part can also contain filler and a curing catalyst for the room-temperature curable silicone composition. The particulate zinc oxide can be added to either the first or second part. The "parts" of these two-part compositions are stored in separate packages to prevent premature curing which can occur if all the ingredients are mixed for too long a time period before the use of the composition.
[0029] Furthermore, the compositions of the present invention can be prepared using either batch or continuous modes of manufacture. Preferably, the ingredients such as silicone polymer, zinc oxide, cure catalyst, crosslinker, adhesion promoter, plasticizers, filler, process aids, and other additives are combined in a continuous compounding extruder to produce the desired sealant composition. Both the "first part"
and the "second part" are prepared in this manner. The continuous compounding extruder can be any continuous compounding extruder such as the twin screw Werner-Pfleiderer extruder, or a Buss, or P.B. Kolcneader extruder.
=
[0030] In the broadest conception of the present invention, all the ingredients may be mixed in the continuous compounding extruder, that is silicone polymer, zinc oxide, _plasticizer, a_condensation catalyst and an adhesion promoter, etc. In such a process, _ _ _ _ _ .7---------whichis;continuousT.theg.extruderAsT,operatedataTrange;_of-.20-1-.tor2002-utmore -_ preferably in the range of 25 to 50 C and the extruder is operated at a partial vacuum so as to remove volatiles during the mixing process.
[0031]
According to one embodiment of the invention, the silicone compositions of the present invention further comprise an alkoxysilane or blend of alkoxysilanes as an adhesion promoter. In one embodiment, the adhesion promoter may be a combination blend of n-2-aminoethy1-3-aminopropyltrimethoxysilane and 1,3,5-tris(trimethoxysilylpropyl)isocyanurate. Other adhesion promoters useful in the present invention include but are not limited to n-2-aminoethy1-3-aminopropyltriethoxysilane, y-aminopropyltriethoxysilane, y-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, bis-y-trimethoxysilypropypamine, N-Phenyl-y-aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, y-aminopropylmethyldiethoxysilane, y- aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylaminopropyltrimethoxysilane, y-glycidoxypropylethyldimethoxysilane, y-glycidoxypropyltrimethoxysilane, y-gl ycidoxyethyltrimethoxysilane, 13-(3,4-epoxycyclohexyl)propyltrimethoxysilane,13-(3,4-epoxycyclohexyl) ethylmethyldimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, f3-cyanoethyltrimethoxysilane, y-acryloxypropyltrimethoxysilane, y-methacryloxypropylmethyldimethoxysilane, 4-amino-3,3,-dimethylbutyltrimethoxysilane, and n-ethyl-3-trimethoxysily1-2-methylpropanamine, and the like.
[0032] The level of incorporation of the alkoxysilane (adhesion promoter) ranges from about 0.1 weight percent to about 20 weight percent. In one embodiment of the invention, the adhesion promoter ranges from about 0.3 weight percent to about weight percent of the total composition. In another embodiment of the invention, the adhesion promoter ranges from about 0.5 weight percent to about 2 weight percent of the total composition.
100331 In one embodiment of the invention the composition of the present invention includes a plasticizer to reduce the modulus of the cured elastomer.
The plasticizer can be polydimethylsiloxane having terminal trioganosiloxy units where the organo groups are methyl, vinyl or phenyl or combinations of these groups. For example, the polydimethylsiloxanes used as plasticizers or modulus reducing agents can normally have a viscosity of from 100 to 100,000 mpa.s measured at 25 C and can be used in amounts up to 80 parts by weight per 100 parts by weight of the polymeric material.
100341 The silicone composition of the present invention may also comprise a filler. Suitable fillers of the present invention include, but are not limited to, ground, precipitated and colloidal calcium carbonates which is treated with compounds such as stearate or stearic acid, reinforcing silicas such as fumed silicas, precipitated silicas, silica gels and hydrophobized silicas and silica gels; crushed and ground quartz, alumina, aluminum hydroxide, titanium hydroxide, diatomaceous earth, iron oxide, carbon black and graphite or clays such as kaolin, bentonite or montmorillonite, talc, mica, nano-clays, organo-clays, and the like.
[00351 In one embodiment of the present invention, the filler is a calcium carbonate filler, silica filler or a mixture thereof. In another specific embodiment of the invention, zinc oxide (d) is added directly to the filler. The type and amount of filler added depends upon the desired physical properties for the cured silicone composition.
In another embodiment of the invention, the amount of filler is from 0 weight percent to ---about-90-weight percent of-the-totakompositionr-In-yet-another embodiment-of---- ¨
¨
- ¨ -invention, -the amount of filler is from about 5 weight percent to about 60 weight percent of the total composition. In still another embodiment of the invention, the amount of filler is from about 10 weight percent to about 40 weight percent of the total composition.
The filler may be a single species or a mixture of two or more species.
[0036] The compositions of the present invention may optionally comprise non-ionic surfactant compound selected from the group of surfactants consisting of polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers of ethylene oxide (E0) and propylene oxide (PO) and copolymers of silicones and polyethers (silicone polyether copolymers), copolymers of silicones and copolymers of ethylene oxide and propylene oxide and mixtures thereof in an 'amount ranging from slightly above 0 weight percent to about 10 weight percent, more preferably from about 0.1 weight percent to about 5 weight percent, and most preferably from about 0.5 weight percent to about 0.75 weight percent of the total composition.
[0037] The compositions of the present invention may be prepared using other ingredients that are conventionally employed in room temperature vulcanizing (RTV) silicone compositions such as colorants and pigments as long as they do not interfere with the desired properties.
[0038] The rapid deep-section curing silicone sealant compositions of the present invention find numerous uses in applications where rapid deep-section curing is essential.
For example, the compositions are used for weather sealing and sealant composition in insulating glass units, or IG units, as elements of windows, skylights, doors and related products, including vehicles. Additional uses of the rapid deep-section curing silicone sealant compositions include conventional curtain wall cladding systems and adjacently jointed window panels, e.g., atrium skylights, glass window walls, and the like.
Together with rapid deep-section curing the present compositions provide the necessary flexibility and resiliency, in the desired application, which provides for expansion and contraction due to various conditions, e.g., temperature variations and movement due to =---=building-settlement-and=thelike. - ¨ - - - - - - - ¨ ---------= - -[0039] The invention is illustrated by the following non-limiting examples:
Preparation of Comparative Example 1 and 2 sealant formulations:
Materials Amount in grams (g) Silanol (30000cst) 34 = OMYACARBTm FT- CaCO3 50 ZnO 0 Double treated fumed silica 6 Dimethylpolysiloxane Plasticizer 10 [0040] Comparative Examples 1 and 2 were prepared without zinc oxide and consisted of the various ingredients displayed in Table 1. Comparative Example I and 2 were prepared the same way in Ross mixer using the following procedure: 34g of silanol polymer was placed in the Ross mixer and lOg of plasticizer was placed in a Ross kettle.
Heat was applied to 100 C. 20 g of Omya CaCO3 was slowly added while mixing.
2g of doubly treated fumed silica was also added. Mixing continued for 15 minutes. The dispersion was checked. Additional 15g of Omya CaCO3 was slowly added along with 2g of doubly treated fumed silica and mixed for 30 minutes. The dispersion was again checked. Another 15g of Omya CaCO3 slowly added to the mix, along with 2 more grains of doubly treated fumed silica and mixing continued for 2 hours. The mixture was transferred to an air-tight container.
100411 Curing Procedure: The mixtures were then blended with catalyst, cross-linker and adhesion promoter with quantities and ingredients displayed in Table 2 and Table 3, respectively, and placed in a Hauschild speed mixer and kept for 9-14 days for aging. The mixtures of Comparative Examples 1 and 2 were then removed and poured in Teflon molds with 1/4" depth.
[0042] Comparative Example 1 was prepared with cross-linker methyl trimethoxy silane (MTMS) and adhesion promoter tris (trimethoxy silyl propyl) isocyanurate (Iso-T) as displayed in Table 2:
Comp. Ex. 1 Hanoi +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker MTMS 0.9 g Adhesion promoter Iso-T 0.2 g [0043] Comparative Example 2 was prepared exactly as Comparative Example 1 except that cross-linker vinyl trimethoxy silane (VTMS) and adhesion promoter Iso-T
were used as displayed in Table 3:
Comp. Ex. 2 Silanol +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker VTMS 0.9 g Adhesion promoter Iso-T 0.2 g [0044] Preparation of Example 1 sealant formulation:
Materials Amount in grams (g) Silanol (30000cst) 33 OMYACARB FT- CaCO3 45 ZnO 5 Double treated fumed silica 6 Dimethylpolysiloxane Plasticizer 10 [0045] Example 1 sealant formulation was prepared with zinc oxide and the -variousingredientsslisplayedin,Table LL_Example_Lwas prepared_in Ross_mixer_using _ _ __ the following procedure: 34g of silanol polymer was placed in a Ross mixer and lOg of plasticizer in a Ross kettle. Heat was applied to 100 C. 15 g of Omya CaCO3, 2g of doubly treated fumed silica, and 5g of zinc oxide were slowly added while mixing.
Mixing continued for 15 minutes. The dispersion was checked. An additional 15g of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture.
Mixing proceeded for 30 minutes. The dispersion was checked. Another 15g of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture.
Mixing continued for 2 hours. The mixture was transferred in an air tight container.
[00461 Curing Procedure: The mixture was then blended with catalyst, cross-linker and adhesion promoter with quantities and ingredients displayed in Table 5, in a Hauschild speed mixer and kept for 9-14 days for aging. The mixture was then taken out and poured in a Teflon mold with 'A" depth.
[0047] Example 1 was prepared cross-linker MTMS and adhesion promoter Iso-T:
Example 1 Silanol +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker MTMS 0.9 g Adhesion promoter Iso-T 0.2 g [00481 The ingredients of Example 2 sealant formulation are displayed in Table 6:
Materials Amount in grams (g) Silanol (30000cst) 34 OMYACARB FT- CaCO3 40 ZnO 10 Double treated fiuned silica 6 ..-Dimethylpolysiloxane-Plasticizer- - - --1-0. ¨ ¨ =
[0049] Example 2 sealant formulation was prepared with zinc oxide and the various ingredients displayed in Table 6. Example 2 was prepared in Ross mixer using the following procedure: 34g of Silanol polymer was placed in a Ross mixer and 10g of plasticizer was placed in a Ross kettle. Heat was applied to 100 C. 15 g of Omya CaCO3, 2g of doubly treated fumed silica, and lOg of zinc oxide were slowly added while mixing. Mixing continued for 15 minutes. The dispersion was checked. An additional lOg of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture. Mixing proceeded for 30 minutes. The dispersion was checked. Another 15g of Omya CaCO3 and 2g of doubly treated fumed silica were slowly added to the mixture.
Mixing continued for 2 hours. The mixture was transferred in an air tight container.
(00501 Curing Procedure: The mixture was then blended with catalyst, cross-linker and adhesion promoter with quantities and ingredients displayed in Table 7, in a Hauschild speed mixer and kept for 9- 14 days for aging. The mixture was then taken out and poured in a Teflon mold with 1/4" depth.
[0051] Example 2 was prepared with cross-linker vinyltrimethoxysilane (VTMS) and adhesion promoter Iso-T and the various ingredients of Table 7:
Example 2 Silanol +
CaCO3 + Plasticizer + Fumed silica 48.5 g Catalyst Titanium isopropoxide ethylacetylacetonate 0.5 g Cross-linker VTMS 0.9 g Adhesion promoter Iso-T 0.2 g [0052] Tack Free Time and Deep Section Cure measurements: After applying Examples 1-2 and Comparative Examples 1-2 in Teflon molds with V," thickness, the surface was made even with an aluminum spacer. Beginning at the time the material was first applied, the surface was checked with a 10g weight to determine if the material is -tackzfree-at45-minute,intervals-Iminimum)Aintilit-is-foundqolbelack=free:--qack-free¨
time data of Examples 1-2 and Comparative Examples 1-2 is presented in Figure 1.
[0053] Deep-section cure was determined by solvent swelling experiments as follows: A weighed portion of the resin in accordance with Examples 1-2 and Comparative Examples 1-2 was obtained from a cut along the thickness of the mold (a sample of about 5 grams from each of Examples 1-2 and Comparative Examples 1-2 was obtained) and allowed to swell in 100m1 of toluene for 3 days. The samples from Example 1-2 and Comparative Examples 1-2 were removed from the toluene and kept for drying under ambient conditions for 3 days. Each sample was weighed again after drying. The difference in weight provides the amount of uncured sample from Example 1-2 and Comparative Examples 1-2 dissolved in toluene. This measurement was obtained at the 6th, 24th and 48th hour after applying the sealant examples in the Teflon mold. The percentage of uncured example was plotted against time.
(0054] Deep-section cure data for Comparative Example 1 and Example 1 are presented in Figure 2, and deep-section cure data for Comparative Example 2 and Example 2 are presented in Figure 3.
(0055] While the process of the invention has been described with reference to certain embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out the process of the invention but that the invention will include all embodiments falling within the scope of the appended claims.
Claims (29)
1.A curable sealant composition comprising:
a) at least one silanol-terminated diorganopolysiloxane;
b) at least one crosslinker for the silanol-terminated diorganopolysiloxane(s);
c) at least one catalyst for the crosslinking reaction;
d) a rapid deep-section curing amount zinc oxide having an average particle size of from 50 to 70 nm, and, optionally, e) at least one additional component of alkyl-terminated diorganopolysiloxane, filler, UV stabilizer, antioxidant, adhesion promoter, cure accelerator, thixotropic agent, plasticizer, moisture scavenger, pigment, dye, surfactant, solvent or biocide, wherein the rapid deep-section curing amount of zinc oxide is present in an amount of at least 1 part by weight per 100 parts by weight of the total amount of curable silicone sealant composition.
a) at least one silanol-terminated diorganopolysiloxane;
b) at least one crosslinker for the silanol-terminated diorganopolysiloxane(s);
c) at least one catalyst for the crosslinking reaction;
d) a rapid deep-section curing amount zinc oxide having an average particle size of from 50 to 70 nm, and, optionally, e) at least one additional component of alkyl-terminated diorganopolysiloxane, filler, UV stabilizer, antioxidant, adhesion promoter, cure accelerator, thixotropic agent, plasticizer, moisture scavenger, pigment, dye, surfactant, solvent or biocide, wherein the rapid deep-section curing amount of zinc oxide is present in an amount of at least 1 part by weight per 100 parts by weight of the total amount of curable silicone sealant composition.
2. The curable sealant composition of Claim 1 wherein the diorganopolysiloxane polymer, component (a), is a silanol terminated diorganopolysiloxane having the formula:
M a D b D'c wherein a = 2, b is equal to or greater than 1, c is zero or a positive integer;
M = (HO)3-x-y R1xR2y SiO1/2, wherein x = 0, 1 or 2 and y is either 0 or I, with the proviso that x y is less than or equal to 2, R1 and R2are monovalent C1 to C60 hydrocarbon radicals;
D = R3R4SiO2/2, wherein R3 and R4 are monovalent C1 to C60 hydrocarbon radicals, and D' = R5R6SiO2/2, wherein R5 and R6 are independently chosen monovalent C1 to C60 hydrocarbon radicals.
M a D b D'c wherein a = 2, b is equal to or greater than 1, c is zero or a positive integer;
M = (HO)3-x-y R1xR2y SiO1/2, wherein x = 0, 1 or 2 and y is either 0 or I, with the proviso that x y is less than or equal to 2, R1 and R2are monovalent C1 to C60 hydrocarbon radicals;
D = R3R4SiO2/2, wherein R3 and R4 are monovalent C1 to C60 hydrocarbon radicals, and D' = R5R6SiO2/2, wherein R5 and R6 are independently chosen monovalent C1 to C60 hydrocarbon radicals.
3. The curable sealant composition of Claim 1 wherein the cross-linkers, component (b), possesses the general formula:
(R7O)(R8O)(R9O)(R10O)Si where R7, R8, R9 and R10 are independently chosen monovalent C1 to C60 hydrocarbon radicals.
(R7O)(R8O)(R9O)(R10O)Si where R7, R8, R9 and R10 are independently chosen monovalent C1 to C60 hydrocarbon radicals.
4. The curable sealant composition of Claim 1 wherein the crosslinker, component (b), is tetra-N-propylsilicate, tetraethylortho silicate, or methyltrimethoxysilane.
5. The curable sealant composition of Claim 1 wherein the catalyst, component (c), is a tin catalyst.
6. The curable sealant composition of Claim 5 wherein the tin catalyst is at least one of dibutyltindilaurate, dibutyltindiacetate, dibutyltindimethoxide, tinoctoate, isobutyltintriceroate, dibutyltinoxide, solubilized dibutyl tin oxide, dibutyltin bis-diisooctylphthalate, bis-tripropoxysilyl dioctyltin, dibutyltin bis-acetylacetone, silylated dibutyltin dioxide, carbomethoxyphenyl tin tris-uberate, isobutyltin triceroate, dimethyltin dibutyrate, dimethyltin di-neodecanoate, triethyltin tartarate, dibutyltin dibenzoate, tin oleate, tin naphthenate, butyltintri-2-ethylhexylhexoate, tinbutyrate, or diorganotin bis .beta.-diketonates.
7. The curable sealant composition of Claim 1 wherein the catalyst, component (c), is a titanium compound.
8. The curable sealant composition of Claim 7 wherein the titantium compound is at least one of Di(isopropoxide) Titanium bis(ethylaceloacetate), Di(isobutoxide) Titanium bis(ethylacetoacetato), Di(n-butoxide) Titanium bis(ethylacetoacetato), 1,3-propanedioxytitanium bis(ethylacetoacetate), Titanium (triethanolaminato)isopropoxide, Bis( triethanolamino) titanium di (methyl diglycolate), Titanium diisopropoxide (bis-2,4-pentanedionate), Titanium ethoxide isopropoxide bis-(2,4-pentanedionate), Titanium bis-(2,4-pentanedionate) (2-EHA), tetra n-butyl titanate, or tetra-isopropyl titanate.
9. The curable sealant composition of Claim 8 wherein the titanium compound is Di(isopropoxide) Titanium bis(ethylacetoacetate).
10. The curable sealant composition of Claim 1 wherein the adhesion promoter is n-2-aminoethyl-3-aminopropyltrimethoxysilane, 1,3,5-tris(trimethoxysilylpropyl)isocyanurate, aminopropyltriethoxysilane, .gamma.-aminopropyltrimethoxysilane, aminopropyltrimethoxysilane, bis-.gamma.-trimethoxysilypropyl)amine, N-Phenyl-.gamma.-aminopropyltrimethoxysilane, triaminofunctionaltrimethoxysilane, .gamma.-aminopropylmethyldiethoxysilane, .gamma.- aminopropylmethyldiethoxysilane, methacryloxypropyltrimethoxysilane, methylarninopropyltrimethoxysilane, .gamma.-glycidoxypropylethyldimethoxysilane, .gamma.-glycidoxypropyltrimethoxysilane, .gamma.-glycidoxyethyltrimethoxysilane, .beta.-(3,4-epoxycyclohexyl)propyltrimethoxysilane, .beta.-(3,4-epoxycyclohexyl)ethylmethyldimethoxysilane, isocyanatopropyltriethoxysilane, isocyanatopropylmethyldimethoxysilane, .beta.-cyanoethyltrimethoxysilane,.gamma.-acryloxypropyltimethoxysilane, .gamma.-methacryloxypropylmethyldimethoxysilane, 4-amino-3,3,-dimethylbutyltrimethoxysilane, n-ethyl-3-trimethoxysilyl-2-methylpropanamine, or mixtures thereof.
19 1. The curable sealant composition of Claim 1 wherein the optional filler is clays, ground calcium carbonate, precipitated calcium carbonate, colloidal calcium carbonate, calcium carbonate treated with compounds stearate or stearic acid; fumed silica, precipitated silica, silica gels, hydrophobized silicas, hydrophilic silica gels, crushed quartz, ground quartz, alumina, aluminum hydroxide, titanium hydroxide, clay, kaolin, bentonite montmorillonite, diatomaceous earth, iron oxide, carbon black, graphite, talc, mica, or mixtures thereof.
12. The curable sealant composition of Claim 1 wherein the surfactant is a non-tonic surfactant and is polyethylene glycol, polypropylene glycol, ethoxylated castor oil, oleic acid ethoxylate, alkylphenol ethoxylates, copolymers of ethylene oxide and propylene oxide or copolymers of silicones and polyethers, copolymers of silicones or copolymers of ethylene oxide and propylene oxide or mixtures thereof in an amount ranging from about 0.1 weight percent to about 10 weight percent.
13. The curable sealant composition of Claim 1 wherein the a diorganopolysiloxane polymer, component (a), ranges from in amount from about weight percent to about 95 weight percent of the total composition.
14. The curable sealant composition of Claim 1 wherein the a diorganopolysiloxane polymer, component (a), ranges from in amount from about weight percent to about 85 weight percent of the total composition.
the curable sealant composition of Claim 1 wherein the a diorganopolysiloxane polymer, component (a), ranges from in amount from about weight percent to about 60 weight percent of the total composition.
16. The curable sealant composition of Claim 1 wherein the amount of the cross-linker, component (b), ranges in amount from about 0.1 weight percent to about 10 weight percent of the total composition.
17. The curable sealant composition of Claim 1 wherein the amount of the cross-linker, component (b), ranges in amount from about 0.3 weight percent to about 5 weight percent of the total composition.
18. The curable sealant composition of Claim 1 wherein the amount of the cross-linker, component (b), ranges in amount from about 0.5 weight percent to about 1.5 weight percent of the total composition.
19. The curable sealant composition of Claim 1 wherein the amount of catalyst, component (c), ranges in amount from about 0.001 weight percent to about 1 weight percent of the total composition.
20. The curable sealant composition of Claim 1 wherein the amount of catalyst, component (c), ranges in amount from about 0.003 weight percent to about 0.5 weight percent of the total composition.
21. The curable sealant composition of Claim 1 wherein the amount of catalyst, component (c), ranges in amount from about 0.005 weight percent to about 0.2 weight percent of the total composition.
22. The curable sealant composition of Claim 1 wherein the amount of zinc oxide, component (d), ranges in amount from about 1 to about 60 weight percent of the total composition.
23. The curable sealant composition of Claim 1 wherein the amount of zinc oxide, component (d), ranges in amount from about 2 to about 30 weight percent of the total composition.
24. The curable sealant composition of Claim 1 wherein the amount of zinc oxide, component (d), ranges in amount from about 5 to about 20 weight percent of the total composition.
25. The curable sealant composition of Claim 1 wherein the amount of filler, ranges in amount from 0 to about 90 weight percent of the total composition.
26. The curable sealant composition of Claim 1 wherein the amount of adhesion promoter ranges in amount from about 0.5 weight percent to about 20 weight percent of the total composition.
27. The curable sealant composition of Claim 11, wherein the clays are nano-clays or organo-clays.
28. The cured composition of claim 1.
29. A cured sealant comprising the curable sealant composition of Claim 1.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US11/728,904 US8217107B2 (en) | 2007-03-27 | 2007-03-27 | Rapid deep-section cure silicone compositions |
| US11/728,904 | 2007-03-27 | ||
| PCT/US2008/003950 WO2008118461A2 (en) | 2007-03-27 | 2008-03-26 | Rapid deep-section cure silicone compositions |
Publications (2)
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| CA2682191A1 CA2682191A1 (en) | 2008-10-02 |
| CA2682191C true CA2682191C (en) | 2016-09-06 |
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| CA2682191A Expired - Fee Related CA2682191C (en) | 2007-03-27 | 2008-03-26 | Rapid deep-section cure silicone compositions |
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| US (1) | US8217107B2 (en) |
| EP (1) | EP2134790B1 (en) |
| JP (1) | JP5324560B2 (en) |
| KR (1) | KR101607631B1 (en) |
| CN (1) | CN101679749B (en) |
| AU (1) | AU2008231295B2 (en) |
| BR (1) | BRPI0809464A2 (en) |
| CA (1) | CA2682191C (en) |
| RU (1) | RU2481363C2 (en) |
| TW (1) | TW200902631A (en) |
| WO (1) | WO2008118461A2 (en) |
| ZA (1) | ZA200906693B (en) |
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| US8501856B2 (en) * | 2007-07-13 | 2013-08-06 | Momentive Performance Materials Inc. | Curable silicon-containing compositions possessing high translucency |
| DE102008055146A1 (en) * | 2008-12-23 | 2010-07-01 | Wacker Chemie Ag | Crosslinkable compositions based on organosilicon compounds |
| CN101792653B (en) * | 2010-03-19 | 2012-10-10 | 江苏明昊新材料科技有限公司 | Sealant for acrylic ester modified solar photovoltaic module and preparation method thereof |
| CN101787260B (en) * | 2010-03-19 | 2012-10-10 | 江苏明昊新材料科技有限公司 | Water vapor transmission resistant silicone sealant and manufacture method thereof |
| CN103013430A (en) * | 2012-12-24 | 2013-04-03 | 成都硅宝科技股份有限公司 | Environment-friendly organosilicone sealant and manufacturing method thereof |
| US10138394B2 (en) | 2014-03-19 | 2018-11-27 | Csl Silicones Inc. | Air-water barrier silicone coatings |
| DE102014212291A1 (en) * | 2014-06-26 | 2015-12-31 | Henkel Ag & Co. Kgaa | Titanium complexes as vulcanization catalysts |
| CN104087056B (en) * | 2014-06-26 | 2017-01-25 | 杭州博创纳米材料有限公司 | Organosilicon-modified hydrophilic activator and application thereof |
| CN104497313A (en) * | 2014-12-05 | 2015-04-08 | 东莞兆舜有机硅新材料科技有限公司 | Non-corrosive organic tin catalyst as well as preparation method and application thereof |
| BR112017023116A2 (en) | 2015-04-30 | 2018-07-10 | Coloplast As | adhesive composition, methods for preparing a moisture curable adhesive composition and releasably or adhesively attaching a medical device to a skin surface, and, packaged product |
| CN105018018A (en) * | 2015-07-01 | 2015-11-04 | 常熟市长江胶带有限公司 | Strong glue for adhesive tapes |
| CN108603075A (en) | 2016-01-27 | 2018-09-28 | 莫门蒂夫性能材料股份有限公司 | Anti-stain characteristic silicone coating composition |
| JP6625453B2 (en) * | 2016-03-14 | 2019-12-25 | Ｊｘｔｇエネルギー株式会社 | Silane compound, rubber composition and tire |
| EP4386246A3 (en) | 2018-10-02 | 2024-09-04 | Borealis AG | Low speed cross-linking catalyst for silane-grafted plastomers |
| CN111500191A (en) * | 2019-01-30 | 2020-08-07 | 佐敦有限公司 | Water-based primer |
| WO2020252772A1 (en) | 2019-06-21 | 2020-12-24 | Dow Silicones Corporation | Method for producing thixotropic curable silicone composition |
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| SU910697A1 (en) * | 1980-07-23 | 1982-03-07 | Московский Филиал Всесоюзного Научно-Исследовательского И Проектного Института Химической Промышленности | Composition based on polystyrene-siloxane rubber |
| JPS57172949A (en) | 1981-04-17 | 1982-10-25 | Kanegafuchi Chem Ind Co Ltd | One-pack composition |
| JPS60202153A (en) * | 1984-03-26 | 1985-10-12 | Toshiba Silicone Co Ltd | Catalyst composition for silicone rubber |
| JP3318338B2 (en) | 1992-02-28 | 2002-08-26 | 東レ・ダウコーニング・シリコーン株式会社 | Method for producing conductive polyorganosiloxane composition |
| US5292606A (en) | 1992-11-30 | 1994-03-08 | Eastman Kodak Company | Fuser roll for fixing toner to a substrate |
| US5786414A (en) * | 1995-12-22 | 1998-07-28 | Toto Ltd. | Building rubber members and method for imparting hydrophilic surface thereto |
| US5733960A (en) | 1996-04-04 | 1998-03-31 | Dow Corning Corporation | Enhanced longevity of surface drying oil on a sealant modified by incorporation of zinc oxide |
| US5973023A (en) | 1996-04-04 | 1999-10-26 | Dow Corning Corporation | Sealants containing fungicides exhibiting less chromophoric development upon exposure to UV by the incorporation of zinc oxide |
| US6258878B1 (en) | 1999-03-29 | 2001-07-10 | Dow Corning Corporation | One-part moisture-curable hydrocarbon polymer composition |
| GB0028254D0 (en) * | 2000-11-21 | 2001-01-03 | Dow Corning Sa | Organopolysiloxane compositions and their preparation |
| JP3916403B2 (en) * | 2001-01-30 | 2007-05-16 | 株式会社スリーボンド | Room temperature curable sealing material composition for automobiles |
| JP4395270B2 (en) * | 2001-05-11 | 2010-01-06 | 信越化学工業株式会社 | Room temperature fast-curing olga polysiloxane composition |
| JP2004292724A (en) * | 2003-03-28 | 2004-10-21 | Shin Etsu Chem Co Ltd | Room temperature curable organopolysiloxane composition |
| RU2249027C1 (en) * | 2003-08-21 | 2005-03-27 | Подшивалин Александр Викторович | Law molecular siloxane rubber-based sealing compound |
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- 2007-03-27 US US11/728,904 patent/US8217107B2/en not_active Expired - Fee Related
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2008
- 2008-03-24 TW TW097110359A patent/TW200902631A/en unknown
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- 2008-03-26 KR KR1020097020287A patent/KR101607631B1/en active IP Right Grant
- 2008-03-26 WO PCT/US2008/003950 patent/WO2008118461A2/en active Application Filing
- 2008-03-26 CA CA2682191A patent/CA2682191C/en not_active Expired - Fee Related
- 2008-03-26 EP EP08742280.4A patent/EP2134790B1/en not_active Not-in-force
- 2008-03-26 AU AU2008231295A patent/AU2008231295B2/en not_active Ceased
- 2008-03-26 BR BRPI0809464-0A patent/BRPI0809464A2/en not_active IP Right Cessation
- 2008-03-26 CN CN200880017726.9A patent/CN101679749B/en not_active Expired - Fee Related
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| AU2008231295B2 (en) | 2013-09-12 |
| CN101679749A (en) | 2010-03-24 |
| TW200902631A (en) | 2009-01-16 |
| CN101679749B (en) | 2016-05-25 |
| AU2008231295A1 (en) | 2008-10-02 |
| WO2008118461A2 (en) | 2008-10-02 |
| US20080242763A1 (en) | 2008-10-02 |
| JP2010522803A (en) | 2010-07-08 |
| EP2134790A2 (en) | 2009-12-23 |
| ZA200906693B (en) | 2010-06-30 |
| US8217107B2 (en) | 2012-07-10 |
| CA2682191A1 (en) | 2008-10-02 |
| WO2008118461A3 (en) | 2009-04-09 |
| RU2009139644A (en) | 2011-05-10 |
| RU2481363C2 (en) | 2013-05-10 |
| KR20090130009A (en) | 2009-12-17 |
| KR101607631B1 (en) | 2016-03-30 |
| BRPI0809464A2 (en) | 2014-09-16 |
| JP5324560B2 (en) | 2013-10-23 |
| EP2134790B1 (en) | 2018-11-14 |
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